CN108417813A - A kind of preparation method of lithium ion battery negative material - Google Patents
A kind of preparation method of lithium ion battery negative material Download PDFInfo
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- CN108417813A CN108417813A CN201810305266.5A CN201810305266A CN108417813A CN 108417813 A CN108417813 A CN 108417813A CN 201810305266 A CN201810305266 A CN 201810305266A CN 108417813 A CN108417813 A CN 108417813A
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- lithium ion
- ion battery
- preparation
- dispersion liquid
- battery negative
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract description 2
- 150000008614 2-methylimidazoles Chemical class 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- -1 zeolite imidazole ester Chemical class 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of preparation method of lithium ion battery negative material, belongs to technical field of lithium ion；The method of the invention is that cabaltous nitrate hexahydrate, nano silica fume, 2 methylimidazoles are separately added into methanol solution, then magnetic stirrer and each self-dispersing 30min of ultrasonic generator are used, two kinds of solution are quickly mixed later, it is stirred at room temperature for 24 hours, the composite material of atropurpureus is obtained after vacuum filtration and drying.Powder is transferred in crucible and is sintered, room temperature is naturally cooled to, obtains the Co/N/C/Si composite powders with porous structure；The Co/N/C/Si composite powders for the porous structure that the method for the invention is prepared have many advantages, such as that granularity is small, uniform, large specific surface area, and the covering property of Si is good；The slow soaking time of heating rate in heat treatment process is shorter, ensures uniformly tiny, the not excessive structural breakdown of particle.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery negative material, belong to technical field of lithium ion.
Background technology
The energy is the lifeblood of current social development, and fossil fuel increasingly depleted and serious problem of environmental pollution make newly
The storage of the energy becomes research hotspot important at present with application；As important energy-storage system, lithium ion battery is in new energy
Technical field is concerned.Currently, to lithium ion battery, more stringent requirements are proposed for the development of the new energy technologies such as electric vehicle,
Wherein energy density and power density are the aspects for especially needing to pay close attention to.The energy density of lithium ion battery is mainly by electrode material
Energy density determine.
Silicon reserves in nature are very abundant (mass content in the earth's crust is 26. 4%, is only second to oxygen), in lithium
Ion battery cathode material application aspect, silicon are considered as most potential cathode material for high capacity lithium ion battery of new generation.
Compared with traditional graphite cathode material, silicon has high specific discharge capacity (4200 mAhg-1, it is the ten of natural graphite
More times)；Compared with lithium metal, since bulk density of the silicon in alloy material is close with lithium, silicon also has very high
Volume and capacity ratio；Different from graphite type material, the height ratio capacity of silicon is derived from the alloying process of silicon lithium, thus silicium cathode material is not
Solvent can occur with electrolyte to be embedded in altogether, and then wider to the scope of application of electrolyte；Compared to Carbon Materials, silicon has higher de-
Intercalation potential can effectively avoid the precipitation of lithium during high rate charge-discharge, can improve the safety of battery.
Due to the influence of bulk effect (expansion rate is about 300%), silicon electrode meeting recurring structure in charge and discharge process is broken
It is bad, cause active material to be peeled off from collector, losing electricity between active material and active material, active material and collector connects
It touches, while constantly forming new solid-phase electrolyte layer (SEI), eventually lead to the low reversible capacity of silicium cathode material, difference is followed
Ring stability and high rate performance；Thus define the use of silicium cathode material.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of lithium ion battery negative material, specifically include following step
Suddenly：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in methanol solution, dispersion liquid A is obtained after agitated and ultrasonic disperse；It will
2-methylimidazole is added in methanol solution, and dispersion liquid B is obtained after agitated and ultrasonic disperse.
（2）Dispersion liquid A and dispersion liquid B are quickly mixed, are aged at room temperature, is then filtered by vacuum, after dry
Obtain powdered substance, silicon, cabaltous nitrate hexahydrate, 2-methylimidazole molar ratio be 1:1:4~3:4:4.
（3）By step（2）Middle powder is calcined to obtain lithium ion battery negative material under inert gas protection.
Preferably, step of the present invention（1）The time of middle ultrasonic disperse is 30min.
Preferably, step of the present invention（2）Middle digestion time is that for 24 hours, drying condition is dry 12h at 60 DEG C.
Preferably, step of the present invention（3）The condition of middle calcining is：It is heated to 600 ~ 800 with the heating rate of 1 ~ 3 DEG C/min
DEG C, it keeps the temperature as 1 ~ 2h, furnace cooling is to room temperature after the completion of heating.
Beneficial effects of the present invention：
（1）The method of the invention is simple for process, at low cost；Product Co/N/C/Si composite lithium ion battery cathode material powder
Have many advantages, such as that granularity is small, uniform, large specific surface area, the covering property of Si is good；Heating rate in heat treatment process is kept the temperature slowly
Time is shorter, ensures uniformly tiny, the not excessive structural breakdown of particle.
（2）Nano Co/N/C/Si composite lithium ion battery cathode material powder is used to prepare lithium ion battery, relative to biography
It unites for silicium cathode material, chemical property increases；In liquid phase reactor, zeolite imidazole ester metal-organic framework exists
Silicon nanoparticle surface self-organization obtains preferable clad, controls volume expansion of the silicium cathode in discharge process and asks
Topic, makes it have preferable cyclical stability in charge and discharge process；During being heat-treated later, negative material is ensureing one
Determine further to be improved the high rate performance of material, together since carbonization obtains certain electric conductivity in the case of structural integrity
When first discharge specific capacity reach 1575mA h g-1Left and right.
Description of the drawings
Fig. 1 is the scanning electricity of the composite material precursor material powder of nanometer ZIF-67 and silicon that present example 3 obtains
Mirror picture.
Fig. 2 is the lithium ion that present example 3 is prepared with nano Co/N/C/Si composite lithium ion battery cathode material powder
The charging and discharging curve of battery.
Fig. 3 is the XRD diagram piece for the ZIF-67 that present example 3 obtains.
Specific implementation mode
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
The preparation method of nano Co described in the present embodiment/N/C/Si composite lithium ion battery cathode materials, specifically includes following step
Suddenly：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in 250ml methanol solutions and are configured to mixed solution, is then stirred in magnetic force
It mixes and ultrasonic disperse 30min obtains dispersion liquid A；2-methylimidazole is added in 250ml methanol solutions, then simultaneously with magnetic agitation
Ultrasonic generator dispersion 30min obtains dispersion liquid B.
（2）By step（1）In dispersion liquid A and dispersion liquid B quickly mix, be aged at room temperature for 24 hours, then very
Sky filters, and methanol is used in combination to clean repeatedly 3 times, and dry 12h obtains the composite material of powdered substance at 60 DEG C；Wherein, silicon, six
Nitric hydrate cobalt, 2-methylimidazole molar ratio be 2:1:4.
（3）By step（2）Powder after middle drying takes out, and is heated under an argon atmosphere with the heating rate of 2 DEG C/min
It 700 DEG C, keeps the temperature as 2h, after the completion of heating, nano Co/N/C/ that grinding distribution after product obtains is taken out in furnace cooling to room temperature
Si composite lithium ion battery cathode material powder.
Electrochemical property test：
1. nano Co/N/C/Si composite lithium ion battery cathode materials the powder and Ketjen black that will be obtained in step (4) gather
Vinylidene (PVDF) is 8 in mass ratio:1:1 ratio, which weighs, to be placed in agate mortar, and appropriate N- methyl -2- pyrroles is added dropwise
Alkanone (NMP) grinding is uniform；It is coated onto on Cu foils, the thickness being coated on Cu foils is 0.15mm, then is placed in vacuum drying
80 DEG C of dryings for 24 hours, then take out pole piece, as cathode in case.
2. metal lithium sheet is as cathode and reference electrode, microporous polypropylene membrane（Celgard2400）For diaphragm, with 1mol/
LiPF6 + EC/DMC/EMC is that electrolyte is assembled into CR2025 in the glove box full of argon gas, moisture less than 2ppm
Stainless steel button cell；Standing tests its charge-discharge performance afterwards for 24 hours.
The scanning electron microscopic picture of the nanocomposite persursor material powder that the present embodiment is prepared as shown in Figure 1,
Synthetic product is to have preferable clad pattern as seen from the figure.
The lithium ion that the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode materials are prepared
Battery maximum specific discharge capacity is 1275mA h g-1.
The lithium ion that the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode materials are prepared
The charge-discharge performance curve of battery is as shown in Fig. 2, it has good discharge performance at higher current densities as seen from the figure.
Embodiment 2
The preparation method of nano Co described in the present embodiment/N/C/Si composite lithium ion battery cathode materials, specifically includes following step
Suddenly：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in 250ml methanol solutions and are configured to mixed solution, is then stirred in magnetic force
It mixes and ultrasonic disperse 30min obtains dispersion liquid A；2-methylimidazole is added in 250ml methanol solutions, then simultaneously with magnetic agitation
Ultrasonic generator dispersion 30min obtains dispersion liquid B.
（2）By step（1）In dispersion liquid A and dispersion liquid B quickly mix, be aged at room temperature for 24 hours, then very
Sky filters, and methanol is used in combination to clean repeatedly 3 times, and dry 12h obtains the composite material of powdered substance at 60 DEG C；Wherein silicon, six
Nitric hydrate cobalt, 2-methylimidazole molar ratio be 2:1:4.
（3）By step（2）Powder after middle drying takes out, and is heated under an argon atmosphere with the heating rate of 2 DEG C/min
It 700 DEG C, keeps the temperature as 1h, after the completion of heating, nano Co/N/C/ that grinding distribution after product obtains is taken out in furnace cooling to room temperature
Si composite lithium ion battery cathode material powder.
Electrochemical property test：It will be in step（4）In obtained nano Co/N/C/Si composite lithium ion battery cathode materials
Powder is assembled into CR2025 button cells according to 1 the method for example；Standing tests its charge-discharge performance afterwards for 24 hours.
The lithium ion that the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode materials are prepared
Battery maximum specific discharge capacity is 1551mA h g-1。
Embodiment 3
The preparation method of nano Co described in the present embodiment/N/C/Si composite lithium ion battery cathode materials, specifically includes following step
Suddenly：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in 250ml methanol solutions and are configured to mixed solution, is then stirred in magnetic force
It mixes and ultrasonic disperse 30min obtains dispersion liquid A；2-methylimidazole is added in 250ml methanol solutions, then simultaneously with magnetic agitation
Ultrasonic generator dispersion 30min obtains dispersion liquid B.
（2）By step（1）In dispersion liquid A and dispersion liquid B quickly mix, be aged at room temperature for 24 hours, then very
Sky filters, and methanol is used in combination to clean repeatedly 3 times, and dry 12h obtains the composite material of powdered substance at 60 DEG C；Wherein silicon, six
Nitric hydrate cobalt, 2-methylimidazole molar ratio be 1:1:4.
（3）By step（2）Powder after middle drying takes out, and is heated under an argon atmosphere with the heating rate of 1 DEG C/min
It 600 DEG C, keeps the temperature as 2h, after the completion of heating, nano Co/N/C/ that grinding distribution after product obtains is taken out in furnace cooling to room temperature
Si composite lithium ion battery cathode material powder.
Electrochemical property test：It will be in step（4）In obtained nano Co/N/C/Si composite lithium ion battery cathode materials
Powder is assembled into CR2025 button cells according to 1 the method for example；Standing tests its charge-discharge performance afterwards for 24 hours.
Lithium ion prepared by the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode material powder
The charging and discharging curve of battery is as shown in Fig. 2, first discharge specific capacity is 1125mAhg-1.
The lithium ion that the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode materials are prepared
The charge-discharge performance curve of battery can be seen that it has good discharge performance at higher current densities.
Embodiment 4
The preparation method of nano Co described in the present embodiment/N/C/Si composite lithium ion battery cathode materials, specifically includes following step
Suddenly：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in 250ml methanol solutions and are configured to mixed solution, is then stirred in magnetic force
It mixes and ultrasonic disperse 30min obtains dispersion liquid A；2-methylimidazole is added in 250ml methanol solutions, then simultaneously with magnetic agitation
Ultrasonic generator dispersion 30min obtains dispersion liquid B.
（2）By step（1）In dispersion liquid A and dispersion liquid B quickly mix, be aged at room temperature for 24 hours, then very
Sky filters, and methanol is used in combination to clean repeatedly 3 times, and dry 12h obtains the composite material of powdered substance at 60 DEG C；Wherein silicon, six
Nitric hydrate cobalt, 2-methylimidazole molar ratio be 3:1:4.
（3）By step（2）Powder after middle drying takes out, and is heated under an argon atmosphere with the heating rate of 3 DEG C/min
It 800 DEG C, keeps the temperature as 2h, after the completion of heating, nano Co/N/C/ that grinding distribution after product obtains is taken out in furnace cooling to room temperature
Si composite lithium ion battery cathode material powder.
Electrochemical property test：It will be in step（4）In obtained nano Co/N/C/Si composite lithium ion battery cathode materials
Powder is assembled into CR2025 button cells according to 1 the method for example；Standing tests its charge-discharge performance afterwards for 24 hours.
The lithium ion that the nano Co that the present embodiment is prepared/N/C/Si composite lithium ion battery cathode materials are prepared
Battery maximum specific discharge capacity is 1205mA h g-1。
The heating rate heated when nano-silicon, cabaltous nitrate hexahydrate, the molar ratio of 2-methylimidazole and heat treatment and heat preservation
Time has a certain impact to product nano Co/N/C/Si composite lithium ion battery cathode materials, and 2-methylimidazole is very few, nanometer
Silica flour is excessive, and temperature height and heating rate are very fast when heat treatment, all the charge-discharge performance of its battery can be caused poor.
Claims (4)
1. a kind of preparation method of lithium ion battery negative material, which is characterized in that specifically include following steps：
（1）Cabaltous nitrate hexahydrate, nano silica fume are added in methanol solution, dispersion liquid A is obtained after agitated and ultrasonic disperse；It will
2-methylimidazole is added in methanol solution, and dispersion liquid B is obtained after agitated and ultrasonic disperse；
（2）Dispersion liquid A and dispersion liquid B are quickly mixed, are aged at room temperature, is then filtered by vacuum, is obtained after dry
Powdered substance, silicon, cabaltous nitrate hexahydrate, 2-methylimidazole molar ratio be 1:1:4~3:4:4；
（3）By step（2）Middle powder is calcined to obtain Co/N/C/Si composite lithium ion battery cathodes under inert gas protection
Material.
2. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that：Step（1）Middle ultrasound
The time of dispersion is 30min.
3. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that：Step（2）Middle ageing
Time is that for 24 hours, drying condition is dry 12h at 60 DEG C.
4. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that：Step（3）Middle calcining
Condition be：Be heated to 600 ~ 800 DEG C with the heating rate of 1 ~ 3 DEG C/min, keep the temperature as 1 ~ 2h, after the completion of heating furnace cooling arrive
Room temperature.
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| CN201810305266.5A CN108417813A (en) | 2018-04-08 | 2018-04-08 | A kind of preparation method of lithium ion battery negative material |
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| CN201810305266.5A CN108417813A (en) | 2018-04-08 | 2018-04-08 | A kind of preparation method of lithium ion battery negative material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461903A (en) * | 2018-09-29 | 2019-03-12 | 昆明理工大学 | A kind of preparation method of lithium-sulfur battery composite cathode material |
| CN109671928A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | A kind of silicon based anode material and preparation method thereof of MOFs carbonization cladding |
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| CN110729472A (en) * | 2019-10-28 | 2020-01-24 | 中科廊坊过程工程研究院 | Silicon-based negative electrode material, preparation method and application thereof |
| CN110867572A (en) * | 2019-11-25 | 2020-03-06 | 天津工业大学 | Preparation method of double-layer carbon-coated silicon composite material |
| CN111261862A (en) * | 2020-01-23 | 2020-06-09 | 荆门市诺维英新材料科技有限公司 | Modified graphite negative electrode material of lithium ion battery and preparation method thereof |
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| CN112349899A (en) * | 2019-09-26 | 2021-02-09 | 贝特瑞新材料集团股份有限公司 | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery |
| CN112678799A (en) * | 2021-01-26 | 2021-04-20 | 四川大学 | Carbon-coated silicon negative electrode material with hollow structure and preparation method thereof |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109461903A (en) * | 2018-09-29 | 2019-03-12 | 昆明理工大学 | A kind of preparation method of lithium-sulfur battery composite cathode material |
| CN109742335B (en) * | 2018-12-06 | 2021-01-12 | 深圳市德方纳米科技股份有限公司 | Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery |
| CN109742335A (en) * | 2018-12-06 | 2019-05-10 | 深圳市德方纳米科技股份有限公司 | Lithium ion battery silicon substrate composite negative pole material and preparation method thereof and lithium ion battery |
| CN109671928A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | A kind of silicon based anode material and preparation method thereof of MOFs carbonization cladding |
| CN110034287A (en) * | 2019-04-10 | 2019-07-19 | 扬州大学 | ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method |
| CN112349899A (en) * | 2019-09-26 | 2021-02-09 | 贝特瑞新材料集团股份有限公司 | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery |
| CN110729472A (en) * | 2019-10-28 | 2020-01-24 | 中科廊坊过程工程研究院 | Silicon-based negative electrode material, preparation method and application thereof |
| CN110867572A (en) * | 2019-11-25 | 2020-03-06 | 天津工业大学 | Preparation method of double-layer carbon-coated silicon composite material |
| CN111261862A (en) * | 2020-01-23 | 2020-06-09 | 荆门市诺维英新材料科技有限公司 | Modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN111403699A (en) * | 2020-03-02 | 2020-07-10 | 吉林师范大学 | Carbon nanotube-containing carbon shell-coated silicon negative electrode material and preparation method thereof |
| CN112678799A (en) * | 2021-01-26 | 2021-04-20 | 四川大学 | Carbon-coated silicon negative electrode material with hollow structure and preparation method thereof |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
| CN114335538A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material, preparation method thereof and lithium battery |
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